Manufacture of detergents



Patented June 11, 1940 PATENT OFFICE MANUFACTURE OF DETERGENTS John F. Olin, Grosse Ile, Mich., assignor to The Sharples Solvents Corporation, Philadelphia,

No Drawing. Application September 28, 1937,

Serial No. 166,094

10 Claims. (Cl. 260 -459) The present invention pertains to the production of sulphur-containing derivatives of paraffin hydrocarbons; and particularly to compounds of this character adapted for use as washing, wet- 5 ting and emulsifying agents or as intermediates adapted for use in the preparation of such agents.

Products obtained by sulphating or sulphonating alcohols or mixtures of alcohols containing ten or more carbon atomsare known to possess 10 excellent detergent properties. Similar products obtained bysulphation or sulphonation of higher olefins are also excellent detergents. Thus, when an olefin containing between 14 and 22 carbon atoms, for example, is sulphated by treatment 15 with concentrated sulphuric acid to produce an alkyl hydrogen sulphate and the alkyl hydrogen sulphate is neutralized to produce the corresponding sodium or potassium salt, the resulting salt has very desirable detergent properties. Similar- 20 ly, when such an olefin is reacted with sulphur trioxide or equivalent reagent and the substituted carbyl sulphate formed as a reaction product is hydrolyzed to produce an alkyl hydroxy sulphonic acid, the resulting acid and its salts are good 25 detergents.

The process of the present invention relates to the manufacture of detergents by a procedure which employs saturated aliphatic hydrocarbons as a source of raw material. Such hydrocarbons 30 may be obtained from petroleum and afford a very inexpensive source of the alkyl radicals forming part of the desired compounds. The

procedure of the invention involves halogenation of the paraflin hydrocarbon to produce mono- 35 halogen derivatives of thehydrocarbon starting material, splitting of the mono-halogen deriva-. tives to produce olefins of corresponding carbon content and ultimate reaction of the olefins formed by the splitting reaction with the sulphurcontaining compounds, such as concentrated sulphuric acid, sulphur trioxide or the reaction product between sulphur trioxide and dioxane.

While a process of this character has definite advantages in the production of the desired 45 detergents, certain serious difficulties are encountered when an attempt is made to put such process into practice on a commercial scale. The

greatest of these difliculties is the problem of production of an olefin fraction of desired carbon 5 content and range by an economical procedure by which this olefin material is adequately separated from contaminating compounds such as alkyl halides and paraffin hydrocarbons.

Let us consider first the procedure which would 55 be involved in a case in which it was desired to produce a detergent containing for the most part sixteen carbon atoms in the alkyl radicals. In such acase, a very careful fractionation of the original hydrocarbon starting material would have to be made in order to get a hydrocarbon mixture within the desired narrow boiling range.

- When this starting material is chlorinated in accordance with standard chlorination procedure to effect chlorination of the majority of the paraffin moleculesa large quantity of dichloride material is necessarily produced. When the mixture of unreacted paraflin hydrocarbon, alkyl monochloride, and alkylen dichloride is subjected to a splitting reaction, the resulting product contains a substantial quantity of the desired olefin, but it contains also some unreacted hydrocarbon, some unsplit alkyl mono-chloride, some unsplit alkylene dichloride and some chlorolefin material.

It is desirable to separate this contaminating material from the desired olefins prior to reaction of .the olefins with the sulphur-containing compound which reacts therewith to produce the desired detergent. This fractionation is, however, a very difficult, and frequently impossible, operation, for the various materials to be separated from the olefins have boiling points very close to the boiling point of the olefin which is to be used.

From the above discussion, it will be seen that the problem of producing an olefin fraction for reacting with sulphur-containing compounds to produce detergents is a difficult one even in cases in which an expensive distillation is performed prior to halogenation of the paraflin fraction to produce the halogenated mixture. In practice, it is desirable from the standpoint of economy to avoid even the expense of a careful distillation to produce a narrow boiling paraffin fraction, since mixtures of hydrocarbons varying widely in carbon content and boiling range form useful sources of the desired alkyl radical. When an attempt is made to halogenate and split a mixture of hydrocarbons varying in content between 16 and 20 carbon atoms, for example, the higher boiling olefins of the mixture have higher boiling points than the lower boiling halogen derivatives, and separation of the olefins from the mixture by distillation is accordingly entirely impossible.

The present invention affords a process by which the above difiiculties are obviated and by which the desired detergents may be very economically produced. In the practice of the invention, a parafiin hydrocarbon fraction of the desired carbon content is first halogenated. The

halogenating operation may be performed by ture of alkyl mono-chlorides and unreacted hydrocarbon is produced, and practically no polychloride derivatives are formed. This chlorina tion operation is preferably conducted in nonmetallic apparatus in order to prevent decomposition of chlorides which are formed, for decomposition of such chlorides would result in the production of olefins during the chlorinating operation, and these olefins would in turn react withchlorine to produce di-chlorides, which are undesired in the practiceof the present invention. Y

In order to avoid conversion of any substantial proportion of the hydrocarbons under treatment to poly-chlorides, the chlorinating operation is preferably discontinued when the increase in the weight of the material under treatment indicates that between 20' and 50% of the hydrocar-,

bons have been converted into mono-chlorides.

At the conclusion of the chlorinating operation, the mixture of unreacted hydrocarbon material and alkyl mono-chlorides is subjected to a splitting operation. This splitting operation may be accomplished in any known manner, such as by .refluxing in the presence of ferric chloride, zinc,

chloride, ferrous chloride, cuprous chloride, cupric chloride, cobalt chloride, cadmium chloride,

antimony chloride, barium chloride, manganese.

chloride, or the'corresponding oxides. It may also be accomplished by reaction of caustic soda or tertiary amines with the halogen derivatives of the mixture. The splitting reaction is performed under conditions of sufilcient severity and for a suflicient length of time to effect substantially complete conversion of the alkyl chlorides into olefins.

At the conclusion, of. this splitting operation, the mixture of olefins and paraflins is treated Y with a sulphur-containing compound which reacts with the olefln to produce the desired detergent. This step of reacting the olefin-containing mixture with a sulphur-containing compound may be performed in accordance with any of the well-known methods of reacting olefins with compounds of this character. Thus, the mixture of olefins and paraflins may be treated with concentrated sulphuric acid to produce a mix-- ture of allryl hydrogen sulphate with unreacted paraflins. Alternatively, the mixture of olefins and paraffins may be reacted with sulphur trioxide to produce substituted carbyl sulphates, andthese substituted carbyl sulphates may then be hydrolyzed to produce hydrox'y' alkyl sulphonic acids, which'may in turn be converted into their alkali metal salts and used as detergents. Instead of reacting the mixture of. olefins and parafilns with sulphur trioxide to produce the substituted carbyl sulphate, this mixture may be reacted with the reaction product of dioxane. with sulphur dioxide to produce the desired substituted carbyl sulphates.

In any case, and regardless of the nature of the specific sulphur-containing compound reacted with the olefins and of the nature of the desired detergent, the parafiin hydrocarbon which is unreacted in the chlorinating step is retained in the reaction mixture until a detergent has been produced. After the detergent has been produced, the hydrocarbon is removed from the reaction mixture. This may be accomplished, for example, by distillation.

The advantages attained in the practice of the invention will now be apparent. As pointed out above, the separation of. the paraflin hydrocarbon or of chlorine derivatives present as contaminating materials after the chlorination and splitting ofthe original paraffin starting material would be in every case difiicult and in many cases impossible.

The present invention involves, on the other hand, substantial avoidance of the formationof poly-chlorides, and practically all of the monochlorides formed are converted into olefins by the splitting reaction. The only contamination remaining with the olefin fraction to be reacted with a sulphur-containing compound to produce the desired detergent is therefore the unreacted No attempt is made to separate this paraflin hydrocarbon prior to the production of. the desired detergent. After the detergent is produced, however, the paraflin hydrocarbon is distilled from the reaction mixture. Thisdistillation can be very readily accomplished at this stage of the operation, since the desired detergents are less volatile than the parafiins to be removed.

The contaminating parafiin hydrocarbon can be removed from any of the sulphur-containing compounds described above. It may, for example, be removed by vacuum distillation from the substituted carbyl sulphate formed as an intermediate compound in the manufacture of hydroxy alkyl sulphonic acids, or from the hydroxy alkyl sulphonic acids themselves, or the salts of such sulphonic acids by steam or vacuum distillation. In case the olefin-containing material is sulphated by treatment with concentrated sulphuric acid, the contaminating paraflin may be distilled from the alkyl hydrogen sulphate under vacuum in order to minimize decomposition of the alkyl hydrogen sulphate. The preferred method of practicing the invention with respect to this type of compound, however, consists in neutralizing these compounds prior to distillation. Thus, the alkyl hydrogen sulphate-containing mixture may be treated with calcium hydroxide to produce 'calcium alkyl sulphate, and convert unreacted sulphuric acid into calcium sulphate, which can, be removed from the reaction mixture by filtration. The step of distilling off unreacted paraflln hydrocarbons is then performed upon the reaction mixture, and can be accomplished without the danger of decomposition of alkyl hydrogen sulphate which would occur if distillation were attempted at an earlier stage.

In case the mixture of olefins and paraflins is treated with sulphur trioxide or equivalent reagent to produce substituted carbyl sulphates, the hydrolysis of these carbyl sulphates may be accomplished simultaneously with the distillation of unreacted'parafilns from the mixture of par-, afiins with the carbyl sulphates by blowing steam through the mixture, preferably under subatmospheric or atmospheric pressure.

In the above discussion, the procedures employed for separating the unreacted parafiins from the detergents have involved distillation. I wish it to be understood that the invention is not limited to the performance of this step by 7| distillation, however, since the separation can in many cases be achieved by other means such .as subsidence under gravity or centrifugal force.

25. hydrolyzed material isneutralized with sodium Example I 1270 grams of a hydrocarbon cut boiling from 310 to 318 C. was chlorinated in liquid phase until it had gained 70 grams in weight. The product was then placed in an autoclave with 500 cc. of 20% sodium hydroxide solution and K heated to 225 C. with stirring. for four hours.

The material is then cooled and the oil consisting of a mixture of unreacted parafllns with oleflns is decanted to separate it from the 15.

aqueous phase.

'Ihemixture of parafiins and olefins is then dried with anhydrous calcium sulphate and treated at room temperature with an aqueous solution containing 336 grams of dioxane sulphotriox ide. The resulting product is then purified by a vacuum distillation with steam, which removes dioxane and unchanged paraffin hydrocarbons. The residual material in the flask is then warmed with 500 cc. of water to complete the hydrolysis of the carbyl. sulphate, and the hydroxide. Upon removal of excess water by evaporation a solid residue remains which consists. of a mixture of sodium sulphate and the sodium salts of the alkyl hydroxy sulphonic acids. This mixture is an effective detergent.

Example II 368 grams of ;.an aliphatic hydrocarbon cut consisting essentially of tridecane and boiling between 225 and 250 C(was chlorinated until it had gained 34.5 grams. The resulting solution of alkyl chlorides'in unchanged paraflins was now refluxed .vigorously for one hour with 4 grams of ferric oxide and then distilled to remove the hydrocarbon mixture of paraflins and olefins from the catalyst. The crude olefin-containing mixture is then dissolved in 125 ccfof butanol and agitated during cooling to a temperature between minus 10 and minus 5 C. 600 grams of concentrated sulphuric acid are added slowly through a dropping funnel. After one hour the reaction is substantially complete and the entire mass is poured into 1,000 cc. of ice water/ The materlal now divides itself into two unch nged paraffln hydrocarbon and a lower The. top layer is removed by decantation and may be rechlorinated and reused. The lower lay r is neutralized with calcium hydroxide in th customary manner and the calcium sulphate resulting from the neutralization is removed by filtration. The calcium alkyl sulphates resulting from neutralization are converted into sodium alkyl sulphates by reaction with sodium carbonate and the resulting mixture of sodium salts is an excellent wetting agent.

Still further modifications will be obvious to those skilled in the art and I do not therefore wish to be limited except by the scope of the subjoined claims.

In the sub-joined claims I wish it to be understood that the term sulphonating agent" is used in a generic sense, and is intended to cover any of the varioussulphur-containing compositions described in this specification for use in the treatment of the mixtures of parafiins and olefins for the manufacture of detergents, whether the compounds produced by the action of said sulphonating agents be the end products ultimately used. as detergents or the intermediate sulphur-containing compounds described in this specification.

I claim: v

1. A process of manufacturing detergents comprising partially chlorinating a paraflin hydrocarbon fraction to produce a mixture of alkyl monochlorides with unreacted parafiins which is substantially free of polychlorides, subjecting said mixture to a splitting reaction and thereby converting the alkyl monochlorides to olefins, treating the mixture of olefins and paraffins so produced with a sulphonating agent to produce a detergent composition by reaction of said sulphonating agent with the olefins of the mixture and thereafter removing the unreacted paraflins from said detergent.

' 2. A process of manufacturing detergents comprising partially chlorinating a paraffin hydrocarbon fraction to produce a mixture of alkyl monochlorides with unreacted paraflins which is substantially free of polychlorides, subjecting said mixture to asplitting reaction and thereby converting the alkyl monochlorides to olefins, treating the mixture of olefins and paraffins so produced with a sulphonating agent to produce a detergent composition by reaction of said sulphonating agent with the olefins of the mixture and thereafter removing the unreacted paraflins by distillation from said detergent.

3. A process of manufacturing detergents comprising partially chlorinating a parafiin hydrocarbon fraction to produce a mixture of alkyl monochlorides with unreacted parafiins which is substantially free of polychlorides, subjecting said mixture to a splitting reaction and thereby converting the alkyl monochlorides to olefins, treating the mixture of olefins and parafiins so produced with a sulphonating agent to produce a detergent by reaction of said sulphonating agent with the olefins of the mixture and thereafter removing the unreacted paraflins by subsidence from said detergent.

4. A process of manufacturing detergents comprising partially chlorinating a paraffin hydrocarbon fraction to produce a mixture of alkyl monochlorides with unreacted paraflins which is substantially free of polychlorides, subjecting said mixture to a splitting reaction and thereby converting the alkyl monochlorides to olefins, treating the mixture of olefins and paraflins so produced with a sulphonating agent consisting of sulphur trioxide to produce a substituted carbyl sulphate detergent by reaction of said sulphonating agent with the olefins of the mixture and thereafter removing the unreacted paraflins from said detergent.

5. A process of manufacturing detergents comprising partially chlorinating a paraflin hydrocarbon fraction to produce a mixture of alkyl monochlorides with unreacted parafiins which is substantially free of polychlorides, subjecting said mixture to a splitting reaction and thereby converting the alkyl monochlorides to olefins, treating the mixture of olefins and paraifins so produced with a sulphonating agent consisting of dioxane sulphur trioxide to produce a substituted carbyl sulphate detergent by reaction of said sulphonating agent with the olefins of the mixture and thereafter removing the unreacted paraifins from said detergent.

6. A process of manufacturing detergents comprising partially chlorinating a paraflsln hydrocarbon fraction to produce a mixture of alkyl monochlorides with unreacted paraflins which is substantially free of polychlorides, subjecting said mixture to a splitting reaction and thereby converting the alkyl monochlorides to olefins, treating the mixture of olefins and paraffins so produced with concentrated sulphuric acid to produce an alkyl' hydrogen sulphate detergent by reaction of said sulphonating agent with the olefins of the mixture and thereafter remmine the unreacted paraffins from said detergent.

'7. A process of manufacturing detergents comprising partially chlorinating a paraffin hydrocarbon fraction to produce a mixture of alkyl monochlorides with unreacted parafilns which is substantially free of poiychlorides, subjecting said mixture to a splitting reaction and thereby converting the alkyl monochlorides to olefins, treating the mixture of olefins and paraifins so produced with a sulphonating agent consisting of sulphur trioxide to produce a substituted carbyl sulphate detergent by reaction of said sulphonating agent with the olefins of the mixture and thereafter hydrolyzing the resulting detergent to produce an hydroxy alkyl sulphonic acid and removing the unreacted parafiins from said hydroxy alkyl sulphonic acid.

- 8. A process of manufacturing detergents comprising partially chlorinating a parafiin hydrocarbon fraction to produce a mixture of alkyl monochlorides with unreacted parafiins which is substantially free of polychlorides, subjecting said mixture to a splitting reaction and thereby converting the alkyl monochlorides to olefins,

treating the mixture of olefins and paramns so produced with a sulphonating agent consisting of v dioxane sulphur trioxide to produce a substituted carbyl sulphate detergent by reaction of said sulphonating agent withthe olefins of the mixture and thereafter hydrolyzing the resulting detergent composition to produce an hydroxy alkyl sulphonic acid and removing the unreactedparafiins from said hydroxy alkyl sulphonic acid.

9. A process of manufacturing'detergents comprising partially chlorinating a paraflin hydrocarbon fraction to produce a mixture of alkyl monochlorides with unreacted paraflins which is substantially free of polychlorides, subjecting said mixture to a splitting reaction and thereby converting the alkyl monochlorides to olefins, treating the mixture of olefins and paraflins so produced with a sulphonating agent consisting of sulphur trioxide to produce a substituted carbyl sulphate detergent and thereafter passing steam through the mixture of carbyl sulphates with unreacted paraflin hydrocarbons to simultaneously hydrolyze said substituted carbyl sulphates and remove unreacted parafiin hydrocarbons fromsaid mixture by distillation.

10. A process of manufacturing detergents comprising partially chlorinating a paraflin hydrocarbon fraction to produce a mixture of alkyl monochlorides with unreacted paraffins which is substantially free of polychlorides, subjecting said mixture to a splitting reaction and thereby converting the alkyl monochlorides to olefins, treating the mixture of olefins and parafllns so produced with a sulphonating agent consisting of dioxane sulphur trioxide to produce a substituted carbyl sulphate detergent and thereafter passing steam through the mixture of carbyl sulphates with unreacted parafiin hydrocarbons to simultaneously hydrolyze said substituted carbyl sulphates and remove unreacted paraffin hydrocarbons from said mixture by distillation.

JOHN F. OLIN. 

